1. Field of the Invention
This invention relates to novel phenoxypyridinemethyl esters of 4-alkenoic acid compounds having pesticidal activity and methods of their preparation.
2. Description of the Prior Art
Esters of isovaleric acid are disclosed in U.S. Pat. No. 4,042,710, including 2-substituted isovalerates having the structural formula I: ##STR1## in which R represents an alkyl group of 1 to 16 carbon atoms (which may be branched), an alkenyl group of up to 6 carbon atoms, or a benzyl group optionally substituted by one or more halogen atoms.
U.S. Pat. Nos. 4,039,680; 4,062,968; and 4,058,622 all disclose esters having the general structure II: ##STR2## where R.sub.7 may be H, CH.sub.3, or CH.sub.2 CH.sub.3 ; R.sub.8 is H or CH.sub.3 ; R.sub.9 is CH.sub.3 ; Z is an alkyl group having from 1 to 3 carbon atoms.
Belgium Pat. No. 862,499 discloses a group of pyrethroidal esters which are characterized by the so-called "Pydrin alcohol" and a class of olefinic esters. The pesticidal phenoxy benzyl pentene carboxylates are prepared by esterifying a phenoxy benzyl alcohol with pentene carboxylic acid. According to the disclosure of Belgium Pat. No. 862,499, esters are prepared using a synthetic method from acids of the general formula III: ##STR3## wherein R.sub.4 =lower alkyl
R.sub.2 and R.sub.5 =H or an alkyl group having from 1-4 carbon atoms R.sub.6 and R.sub.7 =Cl or Br PA1 n is 0, 1 or 2; PA1 Y is 0 or S; PA1 R is H, CN or ethynyl; and PA1 Z is Cl, F or Br. PA1 R.sub.4 and R.sub.5 may be independently hydrogen, a lower alkyl group having from 1 to 5 carbon atoms, polyhaloalkyl, haloalkyl, halogen, a lower alkenyl group having from 2 to 5 carbon atoms, a lower cycloalkyl group having from 3 to 5 carbon atoms, a lower cycloalkenyl group having from 3 to 5 carbon atoms, cyano, nitro, a lower alkoxy group having from 1 to 3 carbon atoms, aryloxy, a lower alkylthio group having from 1 to 3 carbom atoms, arylthio, a lower alkylsulfonyl group having from 1 to 3 carbon atoms, alkylsulfinyl, arylsulfonyl, arylsulfinyl, acylamido, or a lower dialkylamino group having from 1 to 3 carbon atoms; PA1 R.sub.6 may be an alkyl group having from 1 to 5 carbon atoms, branched alkyl, cycloalkyl, alkenyl, branched alkenyl, or cycloalkenyl; PA1 X may be hydrogen, cyano, ethynyl, thioamido, alkyl, cyckoalkyl, alkenyl, polyhaloalkenyl, or dihaloallyl with no more than seven carbon atoms in any one aliphatic group. PA1 R.sub.7, R.sub.8, and R.sub.9 may be individually hydrogen, halogen, nitro, cyano, cycloalkyl, polyhaloalkyl, alkyl, alkoxy, alkenyl, polyhaloalkenyl, cycloalkenyl, phenyl, phenoxy, alkylthio, phenylthio, alkylsulfinyl, phenylsulfinyl, alkylsulfonyl, phenylsulfonyl, acylamino or dialkylamino with no more than seven carbon atoms in any one aliphatic group and two adjacent substituents may be joined by an alkylene, polyhaloalkylene, alkenylene, or polyhaloalkenylene groups to form a 5, 6, or 7-membered ring or by a carbon chain completing a benzene ring fused to the pyridine nucleus; PA1 R.sub.10, R.sub.11, R.sub.12, R.sub.13, and R.sub.14 may individually be halogen, nitro, cyano, hydrogen, alkyl, cycloalkyl, polyhaloalkyl, phenyl phenoxy, alkoxy, alkenyl, polyhaloalkenyl, cycloalkenyl, phenylthio, alkylthio, phenylsulfinyl, alkylsulfonyl, phenylsulfonyl, acylamino or dialkylamino with no more than seven carbon atoms in any one aliphatic group and any two adjacent substituents may also be joined by an alkylene, polyhaloalkylene, alkenylene, polyhaloalkenylene group completing a 5-, 6-, or 7-membered ring or by a carbon chain completing a benzene ring fused to the phenoxy nucleus. PA1 R.sup.7 may be hydrogen PA1 R.sup.8 may be hydrogen, branched or straight chain (C.sub.1 -C.sub.8) alkoxy, or halogen PA1 R.sup.7 and R.sup.8 may occupy adjacent carbons and may be joined by a carbon chain to complete a benzene ring fused to the pyridine nucleus. PA1 R.sup.9 -R.sup.13 may individually be hydrogen, halogen, alkyl, cycloalkyl, polyhaloalkyl, phenyl, phenoxy, alkoxy, alkynloxy, with no more than seven carbons in any one aliphatic chain. Any two substituents may be joined by an alkylene or polyhaloalkylene chain completing a 5, 6, or 7 membered ring or by a carbon chain completing a benzene ring fused to the phenoxy nucleus, with the proviso that: PA1 (1) When R.sup.7 and R.sup.8 are hydrogen that either the 2- and 4- or the 2- and 6-positions of the pyridine nucleus are occupied by the phenoxy and acyloxymethyl radicals; PA1 (2) When R.sup.7 is hydrogen but R.sup.8 is not hydrogen the 2-, 4- and 6-positions of the pyridine nucleus are occupied by R.sup.8, the phenoxy and acyloxymethyl radicals; and PA1 (3) When R.sup.7 and R.sup.8 are joined to complete a benzene ring fused to the pyridine nucleus the 2- and 4-positions of a resulting quinoline or the 1- and 3-positions of a resulting isoquinoline are occupied by the phenoxy and acyloxymethyl radicals.
Belgium Pat. No. 860,687 discloses phenoxybenzyl haloalkenoate esters which are useful as insecticides and acaricides and have the following structural formula IV: ##STR4## wherein X is halogen, Y is halogen or CH.sub.3, Z is CN or ethynyl, and R.sub.1 is H or CH.sub.3.
German Offenlegungsschrift No. 2,810,881 discloses insecticidal phenoxy-or phenylthio-pyridyl methyl ester derivatives prepared from 3,3-dichlorovinyl-2,2-dimethylcyclopropanecarboxylic acid. The cyclopropanecarboxylic acid pyridylmethyl ester derivatives disclosed therein have the following structural formula V: ##STR5## wherein: X is an alkyl group having from 1-4 carbon atoms, an alkoxy group having from 1-4 carbon atoms, an alkylthio group having from 1-4 carbon atoms, an alkylsulphonyl group having from 1-4 carbon atoms, CF.sub.3, 3,4-methylenedioxy, Cl, F or Br;